JPWO2007141994A1 - Oxide sintered body, target, transparent conductive film obtained using the same, and transparent conductive substrate - Google Patents

Abstract

Oxide sintered body containing zinc oxide as a main component and magnesium, target processed, and low resistance transparent conductive material with excellent chemical resistance obtained by DC sputtering or ion plating method Providing membranes and transparent conductive substrates. An oxide sintered body containing zinc oxide and magnesium and having a magnesium content of 0.02 to 0.30 in terms of Mg / (Zn + Mg) atomic ratio; and further, gallium and / or aluminum And the content thereof is more than 0 as a (Ga + Al) / (Zn + Ga + Al) atomic ratio and is 0.08 or less, and the magnesium content is 0.02 to 0 as an Mg / (Zn + Ga + Al + Mg) atomic ratio. .30 oxide sintered body; target obtained by processing these oxide sintered bodies; provided by a transparent conductive film formed on a substrate by sputtering or ion plating using this target .

Description

  The present invention relates to an oxide sintered body, a target, a transparent conductive film obtained using the same, and a transparent conductive substrate. More specifically, the present invention relates to an oxide sintered body mainly composed of zinc oxide and further containing magnesium. The present invention relates to a bonded body, a target obtained by processing the same, a low resistance transparent conductive film excellent in chemical resistance obtained by a direct current sputtering method or an ion plating method, and a transparent conductive substrate.

The transparent conductive film has high conductivity and high transmittance in the visible light region. Transparent conductive films are used for solar cells, liquid crystal display elements, and other light receiving element electrodes, as well as various types of protective films for automobile windows, architectural heat ray reflective films, antistatic films, refrigeration showcases, etc. It is also used as a transparent heating element for fogging.
As the transparent conductive film, tin oxide (SnO ₂ ) -based, zinc oxide (ZnO) -based, and indium oxide (In ₂ O ₃ ) -based thin films are known. As the tin oxide, those containing antimony as a dopant (ATO) and those containing fluorine as a dopant (FTO) are used. As the zinc oxide system, those containing aluminum as a dopant (AZO) and those containing gallium as a dopant (GZO) are used. The transparent conductive film most industrially used is an indium oxide type. Among them, indium oxide containing tin as a dopant is referred to as an ITO (Indium-Tin-Oxide) film, and since a low resistance film can be easily obtained, it has been widely used so far.

The low-resistance transparent conductive film is suitably used for surface elements such as solar cells, liquid crystals, organic electroluminescence, and inorganic electroluminescence, and touch panels. As a method for producing these transparent conductive films, a sputtering method or an ion plating method is often used. In particular, the sputtering method is an effective method when forming a material with a low vapor pressure or when precise film thickness control is required, and since it is very easy to operate, it is widely used industrially. ing.
The sputtering method is a film forming method using a sputtering target as a raw material for a thin film. The target is a solid containing a metal element constituting a thin film to be formed, and a sintered body such as a metal, a metal oxide, a metal nitride, or a metal carbide, or a single crystal depending on the case. In this method, a vacuum apparatus is generally evacuated once and then a rare gas such as argon is introduced. Under a gas pressure of about 10 Pa or less, the substrate is used as an anode and the sputtering target is used as a cathode. An argon plasma is generated by causing a discharge, and the argon cations in the plasma collide with the sputtering target of the cathode, and particles of target components that are repelled by this are deposited on the substrate to form a film.

Sputtering methods are classified according to the method of generating argon plasma, those using high-frequency plasma are called high-frequency sputtering methods, and those using direct-current plasma are called direct-current sputtering methods.
In general, the direct current sputtering method is widely used industrially because the film forming speed is higher than that of the high frequency sputtering method, the power supply equipment is inexpensive, and the film forming operation is simple. However, in contrast to the high-frequency sputtering method, which can form a film even with an insulating target, in the direct current sputtering method, a conductive target must be used.
The film formation rate when the film is formed using the sputtering method is closely related to the chemical bonding of the target material. The sputtering method uses a phenomenon in which an argon cation having kinetic energy collides with a target surface, and a substance on the target surface receives energy and is ejected. The weaker the probability of popping out by sputtering increases.

In a method of forming a transparent conductive film of an oxide such as ITO by sputtering, an alloy target of an element constituting the film (In-Sn alloy in the case of an ITO film) is used in a mixed gas of argon and oxygen. A method of forming an oxide film by a reactive sputtering method, and a mixture of argon and oxygen using an oxide sintered body target of an element constituting the film (In-Sn-O sintered body in the case of an ITO film) There is a method of forming an oxide film by a reactive sputtering method in a gas.
Among these, the method using an alloy target supplies a large amount of oxygen gas during sputtering, but the film formation rate and film characteristics (specific resistance, transmittance) are extremely dependent on the amount of oxygen gas introduced during film formation. It is difficult to stably produce a transparent conductive film having a constant film thickness and desired characteristics. On the other hand, in the method using an oxide target, a part of oxygen supplied to the film is supplied by sputtering from the target, and the remaining deficient oxygen amount is supplied as oxygen gas. Therefore, the dependency of the film formation rate and film characteristics (specific resistance, transmittance) on the amount of oxygen gas introduced during film formation is smaller than when using an alloy target, and the film thickness and characteristics are more stable and constant. Since a transparent conductive film can be produced, an industrial method using an oxide target has been adopted.
Considering productivity and manufacturing cost, the direct current sputtering method is easier to form at high speed than the high frequency sputtering method. That is, when the same power is input to the same target and the film formation rates are compared, the direct current sputtering method is about two to three times faster. Also, the direct current sputtering method is advantageous for productivity because the film formation rate increases as high direct current power is applied. For this reason, industrially, a sputtering target capable of forming a film stably even when high DC power is applied is useful.
On the other hand, ion plating is a method in which the surface of a target material to be a film is locally heated by arc discharge to be sublimated, ionized, and attached to a negatively charged workpiece to form a film. In any case, a film having good adhesion at a low temperature can be obtained, a very wide variety of substrate properties and film properties can be selected, an alloy or a compound can be formed, and the process is environmentally friendly. Ion plating is similar to sputtering, and a transparent conductive film having a constant film thickness and characteristics can be produced more stably by using an oxide tablet.

As described above, indium oxide-based materials such as ITO are widely used industrially, but non-indium-based materials have been demanded in recent years because rare metal indium is expensive.
As described above, zinc oxide materials such as GZO and AZO and tin oxide materials such as FTO and ATO are known as non-indium materials. In particular, zinc oxide-based materials are attracting attention as materials that are low in cost because they are abundantly embedded as resources and that exhibit low specific resistance and high transmittance comparable to ITO. However, the zinc oxide-based transparent conductive film obtained using this has the advantage of being easily dissolved in ordinary acids and alkalis, but on the other hand, it has poor resistance to acids and alkalis, and the etching rate can be controlled. Since it is difficult, high-definition patterning processing by wet etching, which is indispensable for liquid crystal display applications, is difficult. Therefore, its use is limited to solar cells that do not require patterning. For these reasons, it has been a problem to improve the chemical resistance of zinc oxide-based materials.

As an attempt to improve the chemical resistance of the zinc oxide-based transparent conductive film, there are the following examples. In Patent Document 1, zinc (ZnO) is co-added with chromium (Cr) and a donor impurity selected from group III element aluminum (Al) or the like or group IV element silicon (Si) or the like. For the purpose of easy control of the chemical properties of the ZnO-based transparent conductive film without significantly impairing the visible light transmittance and electrical resistivity, a new impurity-codoped ZnO transparent conductive film, a target material for producing the thin film, and Patterning techniques have been proposed.
However, since Cr is known to be highly toxic, it must be considered so as not to adversely affect the environment and the human body. Moreover, since it is necessary to control etching liquid to the temperature range lower than usual called 20-5 degreeC, it is difficult to apply industrially.

  Patent Document 2 proposes an impurity co-doped ZnO transparent conductive film in which cobalt (Co) or vanadium (V) is co-added instead of chromium (Cr), a target material used for manufacturing the thin film, and the like. ing. However, cobalt (Co) is a rare metal like indium (In). Further, since vanadium (V) is toxic, it must be considered so as not to adversely affect the environment and the human body. Moreover, even if any is added, it is difficult to apply industrially because it is necessary to control the etching solution in a temperature range of 20 to 5 ° C., which is lower than usual, as in Patent Document 1.

In addition, there has been proposed a method for obtaining a transparent conductive film that can improve crystallinity and etching characteristics without lowering mobility due to ionized impurity scattering, and has low resistance and excellent workability (see Patent Document 3). Here, an RF magnetron sputtering method is used as a film formation method, and a target in which a MgO chip is pasted on a ZnO: Al ₂ O ₃ 2 wt% sintered body is used to form an MgO-added AZO film (Example) 2) is shown. According to this, an AZO film containing 5% atomic concentration of Mg in a film formed at a substrate temperature of 300 ° C. has a resistivity of 300 μΩcm to 200 μΩcm as compared with a film not containing Mg manufactured under the same conditions. It is described that the etching rate by HCl is improved three times. That is, it is shown that acid resistance, which is one of chemical resistance, is rather lowered by adding Mg. No mention is made of alkali resistance.
Under such circumstances, there is a need for a target that can be used to obtain a transparent conductive film that does not contain toxic components that adversely affect the environment and the human body, and has excellent chemical resistance such as acid resistance and alkali resistance. ing.

JP 2002-075061 A JP 2002-075062 A Japanese Patent Application Laid-Open No. 8-199343

  An object of the present invention is to provide an oxide sintered body containing zinc oxide as a main component and further containing magnesium, a target obtained by processing the oxide, a direct current sputtering method or an ion plating method using the same. An object of the present invention is to provide a low-resistance transparent conductive film excellent in chemical resistance obtained by the above.

  In order to solve the above-mentioned conventional problems, the present inventors have made extensive studies, and in an oxide sintered body containing zinc oxide as a main component and further containing magnesium, the content of magnesium is Mg / (Zn + Mg). By setting the atomic ratio to 0.02 to 0.30, when used as a target such as a direct current sputtering method, it is possible to obtain a zinc oxide-based transparent conductive film having high chemical resistance to acid / alkali and low resistance. Furthermore, the inventors have found that the conductivity of the obtained zinc oxide-based transparent conductive film is further improved by using an oxide sintered body containing a specific amount of gallium and / or aluminum as a target, thereby completing the present invention. It came.

  That is, according to the first invention of the present invention, it contains zinc oxide and magnesium, and the magnesium content is 0.02 to 0.30 as the Mg / (Zn + Mg) atomic ratio. An oxide sintered body characterized by the above is provided.

According to a second aspect of the present invention, in the first aspect, the magnesium content is 0.05 to 0.18 as the Mg / (Zn + Mg) atomic ratio. 1 is provided.
Furthermore, according to the third invention of the present invention, there is provided the oxide sintered body characterized in that the specific resistance is 50 kΩcm or less in the first or second invention.

  On the other hand, according to the fourth invention of the present invention, zinc oxide, magnesium, gallium and / or aluminum are contained, and the content of gallium and / or aluminum is (Ga + Al) / (Zn + Ga + Al) atoms. Provided is an oxide sintered body having a number ratio exceeding 0 and not more than 0.09, and a magnesium content of 0.02 to 0.30 as an Mg / (Zn + Ga + Al + Mg) atomic number ratio. The

According to a fifth invention of the present invention, in the fourth invention, the magnesium content is 0.05 to 0.18 as Mg / (Zn + Ga + Al + Mg) atomic ratio. A sintered body is provided.
According to the sixth invention of the present invention, in the fourth invention, the content of gallium and / or aluminum is 0.01 to 0.08 as a (Ga + Al) / (Zn + Ga + Al) atomic ratio. An oxide sintered body characterized by the above is provided.
According to the seventh invention of the present invention, in the fourth invention, the content of gallium and / or aluminum is 0.035 to 0.08 as (Ga + Al) / (Zn + Ga + Al) atomic ratio, And magnesium content is 0.098-0.18 as Mg / (Zn + Ga + Al + Mg) atomic number ratio, and the oxide sintered compact characterized by the above-mentioned is provided.
According to the eighth invention of the present invention, in any one of the fourth to seventh inventions, the peak intensity ratio by X-ray diffraction measurement represented by the following formula (A) is 15% or less. An oxide sintered body characterized by the above is provided.
I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] / I [ZnO (101)] × 100 (%) (A)
(Where I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] is the (311) peak intensity and MgAl ₂ O ₄ phase of the complex oxide MgGa ₂ O ₄ phase having a cubic rock salt structure (311) is the sum of peak intensities, and I [ZnO (101)] represents the (101) peak intensity of the zinc oxide phase having a hexagonal wurtzite structure)
Moreover, according to the ninth invention of the present invention, there is provided an oxide sintered body characterized in that the specific resistance is 5 kΩcm or less in any of the fourth to eighth inventions.
Furthermore, according to a tenth aspect of the present invention, there is provided an oxide sintered body characterized in that the magnesium oxide phase is not substantially contained in any one of the first to ninth aspects.

According to an eleventh aspect of the present invention, there is provided an oxide sintered body characterized by being obtained by molding and sintering by a hot press method in any one of the first to tenth aspects.
On the other hand, according to the twelfth aspect of the present invention, there is provided a target obtained by processing the oxide sintered body according to any one of the first to eleventh aspects.
According to a thirteenth aspect of the present invention, there is provided the target according to the twelfth aspect, wherein the density is 5.0 g / cm ³ or more and the target is used in a sputtering method.
Furthermore, according to the fourteenth aspect of the present invention, there is provided the target according to the twelfth aspect, wherein the density is 3.5 to 4.5 g / cm ³ and the target is used for an ion plating method. Is done.

  On the other hand, according to the fifteenth aspect of the present invention, there is provided a transparent conductive film formed on a substrate by sputtering or ion plating using the targets according to the twelfth to fourteenth aspects.

According to the sixteenth aspect of the present invention, in the fifteenth aspect, zinc oxide and magnesium are contained, and the magnesium content is 0.02 to Mg / (Zn + Mg) atomic ratio. A transparent conductive film characterized by being 0.30 is provided.
According to the seventeenth aspect of the present invention, in the fifteenth aspect, zinc oxide, magnesium, gallium and / or aluminum are contained, and the content is (Ga + Al) / (Zn + Ga + Al) atomic ratio. Thus, a transparent conductive film is provided, wherein the content is greater than 0 and less than or equal to 0.09, and the magnesium content is 0.02 to 0.30 as the Mg / (Zn + Ga + Al + Mg) atomic ratio.
According to an eighteenth aspect of the present invention, in the seventeenth aspect, the magnesium content is 0.05 to 0.18 as the atomic ratio of Mg / (Zn + Ga + Al + Mg). A membrane is provided.
According to the nineteenth aspect of the present invention, in the seventeenth or eighteenth aspect, the gallium and / or aluminum content is 0.01 to 0.08 as a (Ga + Al) / (Zn + Ga + Al) atomic ratio. A transparent conductive film is provided.
According to the twentieth aspect of the present invention, in the seventeenth aspect, the gallium and / or aluminum content is 0.035 to 0.08 in terms of (Ga + Al) / (Zn + Ga + Al) atomic ratio, And the content of magnesium is 0.098-0.18 as Mg / (Zn + Ga + Al + Mg) atomic ratio, and the transparent conductive film characterized by the above-mentioned is provided.
According to the twenty-first aspect of the present invention, in the fifteenth to twentieth aspects, an X-ray diffraction measurement consisting mainly of a zinc oxide phase having a hexagonal wurtzite structure and represented by the following formula (B): A transparent conductive film is provided in which the peak intensity ratio is 50% or more. In the formula, I [ZnO (002)] is a (002) peak intensity of a zinc oxide phase having a hexagonal wurtzite structure, and I [ZnO (100)] is an oxidation having a hexagonal wurtzite structure. The (100) peak intensity of the zinc phase is shown.
I [ZnO (002)] / (I [ZnO (002)] + I [ZnO (100)]) × 100 (%) (B)
Furthermore, according to a twenty-second invention of the present invention, there is provided a transparent conductive film characterized in that, in the fifteenth to twenty-first inventions, a zinc oxide phase having a cubic rock salt structure is substantially not contained.

According to a twenty-third aspect of the present invention, there is provided the transparent substrate, and the transparent conductive film according to any one of the fifteenth to twenty-second inventions formed on one or both sides of the transparent substrate, the transparent The substrate is either a glass plate, a quartz plate, a resin plate or a resin film whose one or both sides are covered with a gas barrier film, or a resin plate or a resin film in which a gas barrier film is inserted. A transparent conductive substrate is provided.
According to a twenty-fourth aspect of the present invention, in the twenty-third aspect, the gas barrier film is selected from the group consisting of a silicon oxide film, a silicon oxynitride film, a magnesium aluminum oxide film, a tin oxide film, and a diamond-like carbon film. A transparent conductive substrate characterized in that it is at least one selected is provided.
Furthermore, according to a twenty-fifth aspect of the present invention, in the twenty-third aspect, the resin plate or resin film has polyethylene terephthalate, polyethersulfone, polyarylate, polycarbonate, or a surface thereof covered with an acrylic organic material. A transparent conductive substrate characterized by comprising a laminated structure is provided.

According to the present invention, since the oxide sintered body contains zinc oxide as a main component and further contains a specific amount of magnesium, if this is used as a sputtering target, arc discharge does not occur even in direct current sputtering, It becomes possible to form a transparent conductive film excellent in chemical resistance. Furthermore, the conductivity of the transparent conductive film obtained can be further improved by using an oxide sintered body containing a specific amount of gallium and / or aluminum.
Further, the oxide sintered body of the present invention can be similarly used as a tablet for ion plating, and high-speed film formation is possible. The zinc oxide-based transparent conductive film of the present invention thus obtained is controlled to an optimal composition and crystal phase, and thus exhibits excellent chemical resistance without greatly impairing visible light transmittance and electrical resistivity. It is industrially extremely useful as a transparent conductive film that does not use relatively expensive indium, and can be suitably used as a transparent conductive substrate using the transparent conductive film.

FIG. 1 is a graph showing the results of identifying the generation phase of the transparent conductive film by X-ray diffraction measurement.

  Hereinafter, the oxide sintered body of the present invention, the target, the transparent conductive film obtained using the target, and the transparent conductive substrate will be described in detail.

1. Oxide Sintered Body The oxide sintered body of the present invention contains zinc oxide and magnesium, and the magnesium content is 0.02 to 0.30 as the Mg / (Zn + Mg) atomic ratio. It is characterized (hereinafter also referred to as a first oxide sintered body).
The oxide sintered body of the present invention contains zinc oxide, magnesium, gallium and / or aluminum, and the content of gallium and / or aluminum is (Ga + Al) / (Zn + Ga + Al) atoms. The ratio is more than 0 and not more than 0.08, and the magnesium content is 0.02 to 0.30 as the Mg / (Zn + Ga + Al + Mg) atomic ratio (hereinafter referred to as the second oxidation). Also called a sintered product.

(1) First oxide sintered body The first oxide sintered body of the present invention is an oxide containing zinc oxide as a main component and further containing a specific amount of magnesium. The content of magnesium is a ratio of 0.02 to 0.30 in terms of the Mg / (Zn + Mg) atomic ratio. Since magnesium is contained in the above composition range, when this oxide sintered body is used as a target raw material, the chemical resistance of the transparent conductive film mainly composed of zinc oxide formed by sputtering or the like is improved. To do.

  Here, the chemical resistance of the transparent conductive film is divided into acid resistance and alkali resistance, and the relationship with the magnesium content is described. When the magnesium content is less than 0.02 in terms of the Mg / (Zn + Mg) atomic ratio, both the acid resistance and alkali resistance of the resulting transparent conductive film are insufficient. As will be described in detail below, the crystallinity of the film is lowered, so that sufficient acid resistance cannot be obtained. However, the alkali resistance is better as the magnesium content is increased, and is sufficiently good even when it exceeds 0.30. On the other hand, if the magnesium content exceeds 0.30, the crystallinity of the film decreases, and the specific resistance also increases. In order to enable direct current (DC) sputtering, the specific resistance needs to be 50 kΩcm or less, and the tendency for the specific resistance to increase is not preferable. In order to reduce the specific resistance, it is desirable to add, for example, sintering in a reducing atmosphere or heat treatment during the production of the oxide sintered body. For this reason, the particularly preferable magnesium content is a ratio of 0.05 to 0.18 in terms of the Mg / (Zn + Mg) atomic ratio.

In the present invention, the oxide sintered body is mainly composed of a zinc oxide phase. This zinc oxide phase refers to a hexagonal wurtzite structure described in JCPDS card 36-1451, and oxygen deficiency. Also included are zinc-deficient non-stoichiometric compositions. Magnesium, which is an additive element, is usually dissolved in the zinc site of the zinc oxide phase.
In the oxide sintered body of the present invention, it is preferable that the oxide sintered body does not contain the magnesium oxide phase described in JCPDS card 45-0946. If magnesium is not dissolved in the zinc oxide phase and is contained in the oxide sintered body as a magnesium oxide phase that is not a good conductor, it will be charged by the irradiation of argon ions during sputtering, causing dielectric breakdown. This is because discharge is generated and stable film formation by direct current (DC) sputtering becomes difficult.

The density of the oxide sintered body is not particularly limited, but when the sputtering target is used, it is preferably 5.0 g / cm ³ or more. When the density is lower than 5.0 g / cm ³ , DC sputtering becomes difficult and problems such as remarkable generation of nodules occur. Nodules are fine protrusions that occur in the erosion part of the target surface as a result of sputtering. Abnormal discharge and splash occur due to the nodules, which causes coarse particles ( Particles) float, and the particles adhere to the film in the middle of the film formation and cause the quality to deteriorate. On the other hand, when the film is formed by the ion plating method, cracking occurs when the sintered body density is too high, and therefore a relatively low density in the range of 3.5 to 4.5 g / cm ³ is preferable.

  The oxide sintered body of the present invention is mainly composed of a zinc oxide phase in which magnesium is dissolved, and has a specific resistance of 50 kΩcm or less, preferably 30 kΩcm or less, more preferably 10 kΩcm or less. ) Stable film formation by sputtering is possible. In addition to magnesium, other additive elements (for example, indium, titanium, tungsten, molybdenum, iridium, ruthenium, rhenium, and the like) may be included as long as the object of the present invention is not impaired. Moreover, for the purpose of improving the sintered density of the oxide sintered body, for example, a small amount of titanium oxide, zirconium oxide, germanium oxide, indium oxide, tin oxide or the like may be added as a sintering aid. However, it is necessary to add the sintering aid in a range that does not affect the various characteristics of the film, and it is preferably in the range of 0.1 to 0.3 wt% in terms of oxide composition.

(2) Second oxide sintered body The second oxide sintered body of the present invention contains zinc oxide, magnesium, gallium and / or aluminum, and contains gallium and / or aluminum. The amount is more than 0 as a (Ga + Al) / (Zn + Ga + Al) atomic ratio and not more than 0.09, and the magnesium content is 0.02 to 0.30 as an Mg / (Zn + Ga + Al + Mg) atomic ratio. Features.

In the oxide sintered body, gallium and / or aluminum that contributes to improvement in conductivity must be contained in the above composition range. When the total content of gallium and / or aluminum exceeds 0.09 in terms of the (Ga + Al) / (Zn + Ga + Al) atomic ratio, the transparent conductive film formed using the target made from the oxide sintered body of the present invention is used. Since the crystallinity of the film is lowered, the specific resistance is increased, and the chemical resistance, particularly the acid resistance is lowered.
When both the aluminum and gallium are contained in the oxide sintered body, the content of aluminum and gallium is 3.2 to 6.5 atomic percent in terms of (Al + Ga) / (Zn + Al + Ga) atomic ratio, and The content of aluminum and gallium is 30 to 70 atomic% in terms of Al / (Al + Ga) atomic ratio, and the content of aluminum in the spinel-type oxide phase formed in the oxide sintered body is Al // (Al + Ga) atomic ratio is preferably 10 to 90 atomic%. If an oxide sintered body that does not satisfy these composition ranges, that is, an oxide sintered body containing excess aluminum or gallium, is used as a target for direct current sputtering, abnormal discharge is likely to occur in the case of aluminum, or gallium This is because particles are likely to be generated. In particular, when high direct-current power is applied or when sputtering is performed for a long time, such generation is remarkable. The cause of abnormal discharge that occurs in the case of aluminum is considered to be in the spinel type oxide phase formed in the above oxide sintered body, and by making aluminum and gallium coexist in this phase in the above composition range. Solved. The problem of particles that occurs in the case of gallium is solved by a similar technique.
In addition, as described above, when the magnesium content is less than 0.02 in terms of the Mg / (Zn + Ga + Al + Mg) atomic ratio, the transparent conductive film cannot obtain sufficient acid resistance and alkali resistance, and exceeds 0.30. In addition, sufficient acid resistance cannot be obtained, and the specific resistance increases, which is not preferable. Further, in order to obtain a low specific resistance, and excellent acid resistance and alkali resistance, the total content of gallium and / or aluminum is 0.01 to 0.08 in terms of (Ga + Al) / (Zn + Ga + Al) atomic ratio, magnesium. It is even more preferable that the content of is in the range of 0.05 to 0.18 in terms of the Mg / (Zn + Ga + Al + Mg) atomic ratio.
Furthermore, in order to obtain a much lower specific resistance and excellent acid resistance and alkali resistance, the total content of gallium and / or aluminum is 0.035 to 0.005 in terms of (Ga + Al) / (Zn + Ga + Al) atomic ratio. It is important that the content of magnesium is set to 08 and the content of magnesium is in the range of 0.098 to 0.18 in terms of Mg / (Zn + Ga + Al + Mg) atomic ratio. The reason why this limited composition range is useful will be described later in the section of the transparent conductive film.

  In the present invention, the oxide sintered body is mainly composed of a zinc oxide phase. This zinc oxide phase refers to a hexagonal wurtzite structure described in JCPDS card 36-1451, and oxygen deficiency. Also included are zinc-deficient non-stoichiometric compositions. The additive elements gallium, aluminum, and magnesium are usually dissolved in the zinc site of the zinc oxide phase.

  When composed mainly of gallium and / or aluminum and a zinc oxide phase in which magnesium is dissolved in the above composition range, it is possible to obtain conductivity of 5 kΩcm or less, more preferably 1 kΩcm or less. In film formation by direct current (DC) sputtering, higher power can be applied, and high-speed film formation is possible. In addition to magnesium, other additive elements (for example, indium, titanium, tungsten, molybdenum, iridium, ruthenium, rhenium, and the like) may be included as long as the object of the present invention is not impaired. Moreover, for the purpose of improving the sintered density of the oxide sintered body, for example, a small amount of titanium oxide, zirconium oxide, germanium oxide, indium oxide, tin oxide or the like may be added as a sintering aid. However, it is necessary to add the sintering aid in a range that does not affect the various characteristics of the film, and it is preferably in the range of 0.1 to 0.3 wt% in terms of oxide composition.

Further, the oxide sintered body of the present invention includes a composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium described in JCPDS card 10-0113, and magnesium and aluminum described in JCPDS card 21-1152. The composite oxide MgAl ₂ O ₄ phase is defined by the following formula (A), the peak intensity due to (101) of the zinc oxide phase having a hexagonal wurtzite structure obtained by X-ray diffraction measurement, and cubic crystal The ratio of the peak intensity due to (311) of the complex oxide MgGa ₂ O ₄ phase having a rock salt structure to the peak intensity due to (311) of the MgAl ₂ O ₄ phase is 15% or less, and further 10% or less. preferable. Most preferably, the composite oxide MgGa ₂ O ₄ phase and the composite oxide MgAl ₂ O ₄ phase are not included.
I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] / I [ZnO (101)] × 100 (%) (A)

Here, I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] is the (311) peak intensity of the complex oxide MgGa ₂ O ₄ phase having a cubic rock salt structure obtained by X-ray diffraction measurement. Is the sum of (311) peak intensities of MgAl ₂ O ₄ phase, and I [ZnO (101)] is the (101) peak intensity of the zinc oxide phase having a hexagonal wurtzite structure obtained by X-ray diffraction measurement Is shown.

When the composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium and the composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum are present in the oxide sintered body beyond the above strength ratio range, Since a zinc oxide phase having a cubic rock salt structure is formed, the acid resistance is remarkably lowered. Further, when the content of magnesium is large, especially when the Mg / (Zn + Ga + Al + Mg) atomic ratio is in the range of 0.10 to 0.30, the composite oxide MgGa ₂ O containing magnesium oxide or magnesium and gallium is used. _Since it becomes easy to produce _four phases and a composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum, it is necessary to manufacture an oxide sintered body by a process set to appropriate conditions as described in the next section.
The density of the oxide sintered body is not particularly limited, but for the above reasons, it is preferably 5.0 g / cm ³ or more when used as a sputtering target. In the case of an ion plating target, a relatively low density in the range of 3.5 to 4.5 g / cm ³ is preferable.

2. Production of Oxide Sintered Body In the present invention, the oxide sintered body is not particularly limited by the production method. For example, it can be performed by a method including a step of forming a molded body from raw material powder and a step of putting the molded body in a sintering furnace and sintering it. In the oxide sintered body of the present invention, it is desirable that the magnesium oxide phase is not generated. However, among the production conditions, for example, it largely depends on the particle size of the raw material powder, the mixing conditions, and the firing conditions. .

(1) Formation of molded body In the step of forming a molded body from the raw material powder, if it is the first oxide sintered body, the magnesium oxide powder is added to the zinc oxide powder as the raw material powder, and the second oxide is sintered. If it is a ligation, the gallium oxide powder and / or aluminum oxide powder containing the group III element of a periodic table are added and mixed with this. The group III element in the periodic table greatly contributes to a high-density and highly conductive sintered body.

The raw material powder is not particularly limited by the average particle diameter, but it is desirable to use a powder having an average particle diameter of 3 μm or less, particularly 1 μm or less. For example, ball mill mixing is performed using zinc oxide powder having an average particle diameter of 1 μm or less, magnesium oxide powder having an average particle diameter of 1 μm or less, and gallium oxide powder having an average particle diameter of 1 μm or less and / or aluminum oxide powder having an average particle diameter of 1 μm or less. Use of the mixed powder performed for 24 hours or more is effective in suppressing the formation of the magnesium oxide phase in the oxide sintered body.
In particular, when the Mg / (Zn + Ga + Al + Mg) atomic ratio is in the range of 0.10 to 0.30, not only the magnesium oxide phase but also the composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium, and magnesium and aluminum It is preferable to perform ball mill mixing for 36 hours or more, although it depends on the form of the raw material powder because a composite oxide MgAl ₂ O ₄ phase containing oxygen is easily generated. When the average particle size exceeds 3 μm or the mixing time is less than 24 hours, the components are not mixed uniformly, and gallium and / or aluminum and magnesium are not easily dissolved in the above composition range in the zinc oxide phase. Therefore, a magnesium oxide phase, or a composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium, and a composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum are contained in the zinc oxide phase of the oxide sintered body obtained for that purpose. It is not preferable because it exists.

  In general, in the case of making a target oxide sintered body that can stably form a film in a zinc oxide-based oxide sintered body, it is preferable to use an oxide of an element added to zinc oxide as a raw material powder, It can also be produced from a raw material powder in which a zinc oxide powder and a metal powder of another element to be added are combined. However, if the metal powder (particles) added to the oxide sintered body is present, the metal particles on the surface of the target melt during the film formation, which increases the difference in composition between the target and the film. There is no.

The raw material powder is mixed and stirred using a known apparatus, and after adding and granulating a binder (for example, PVA) etc., the raw material powder is adjusted to a range of 10 to 100 μm, and the granules thus obtained are, for example, 1000 kg / cm ³ or more. Press molding at a pressure of Subsequently, the raw material powder is press-molded with a metal mold to compress the powder, resulting in high-concentration condensed particles, an improved bulk density, and a higher-density molded body can be obtained. At a pressure lower than 1000 kg / cm ³ , the bulk density is not sufficiently improved, and a satisfactory density improvement effect cannot be expected.

(2) Sintering of molded body The sintering process following the molding process is a process in which the molded body is put into a sintering furnace and sintered, and the firing method may be a simple normal pressure firing method, The law may be used.

In the case of the normal pressure firing method, for example, in an atmosphere in which oxygen is introduced into the atmosphere in the sintering furnace, the firing is performed at 1100 ° C. to 1500 ° C., preferably 1200 ° C. to 1500 ° C., for 10 to 30 hours, preferably 15 to 25 hours. Conclude. When the temperature is lower than 1100 ° C., the progress of sintering becomes insufficient, the density of the sintered body becomes low, and the resistance value becomes high. In addition, a target manufactured from the obtained sintered body is not preferable because a film formation rate is slow and defects such as abnormal discharge occur during sputtering. When the temperature is raised to the sintering temperature, it is preferable to set the rate of temperature rise to a range of 0.2 to 5 ° C./min in order to prevent cracking of the sintered body and advance the binder removal. Further, in order to sufficiently dissolve magnesium in the zinc oxide lattice so that the magnesium oxide phase is not formed in the sintered body, the range is 0.2 ° C./min or more and less than 1 ° C./min. Is even more preferred. If it is less than 0.2 ° C./min, it may not be suitable for actual operation, and there may be a problem that crystal growth of the sintered body becomes remarkable. Moreover, you may heat up to sintering temperature combining a different temperature increase rate as needed. In the temperature raising process, the binder may be held for a certain time at a specific temperature for the purpose of progressing debinding and sintering. After sintering, when introducing oxygen, the introduction of oxygen is stopped, and the temperature can be lowered to 1000 ° C. at a rate of 0.2-5 ° C./min, particularly 0.2 ° C./min. preferable.
As described above, according to the process as described above, using a fine raw material powder, performing sufficient mixing and sintering at a sufficient sintering temperature at which diffusion proceeds, magnesium oxide powder does not remain, That is, the magnesium oxide phase does not exist in the oxide sintered body. However, the composite oxide or the like may be generated depending on the composition.

  Compared with the above-mentioned normal pressure firing method, the hot press method forms and sinters the raw material powder of the oxide sintered body in a reducing atmosphere, so the oxygen content in the sintered body can be reduced. It is. Since the zinc oxide-based transparent conductive film has extremely high affinity between zinc and oxygen, when the oxygen content in the sintered body is high, various characteristics such as specific resistance are deteriorated. The hot press method does not reach the atmospheric pressure firing method in terms of production cost, but is useful when the required characteristics are high with respect to the transparent conductive film. In the present invention, it is particularly useful to produce an oxide sintered body by adopting a hot press method in order to obtain a transparent conductive film having a strong crystal orientation.

An example of the manufacturing conditions of the oxide sintered body by the hot press method of the present invention will be given. Specifically, zinc oxide powder having an average particle diameter of 1 μm or less, magnesium oxide powder having an average particle diameter of 1 μm or less, and gallium oxide powder having an average particle diameter of 1 μm or less and / or aluminum oxide powder having an average particle diameter of 1 μm or less are used as raw material powders. Are mixed to a predetermined ratio. The blended raw materials are uniformly mixed with a dry ball mill, a V blender, etc., then powdered into a carbon container and sintered by a hot press method. The sintering temperature may be 1000 to 1200 ° C., the pressure may be 2.45 MPa to 29.40 MPa (25 kgf / cm ^{2 to} 300 kgf / cm ² ), and the sintering time may be about 1 to 10 hours. The atmosphere during hot pressing is preferably in an inert gas such as Ar gas or in a vacuum. In the case of a sputtering target, more preferably, the sintering temperature is 1050 to 1150 ° C., the pressure is 9.80 MPa to 29.40 MPa (100 kgf / cm ^{2 to} 300 kgf / cm ² ), and the sintering time is 1 to 3 hours. That's fine. In the case of an ion plating target, more preferably, the sintering temperature is 1000 to 1100 ° C., the pressure is 2.45 MPa to 9.80 MPa (25 kgf / cm ^{2 to} 100 kgf / cm ² ), and the sintering time is 1 to 1. What is necessary is just 3 hours.

3. Target The oxide sintered body produced by the above method is processed by surface grinding or the like to obtain a predetermined dimension, and then adhered to a backing plate to obtain a target (also referred to as a single target). it can. If necessary, several sintered bodies may be divided into divided shapes to form a large area target (also referred to as a composite target).

The target includes a sputtering target and an ion plating target. In the ion plating method, such a material is sometimes referred to as a tablet, but in the present invention, it is collectively referred to as a target. Its density, if the sputtering target is at 5.0 g / cm ³ or more, if ion plating target, it is preferable that 3.5~4.5g / cm ^3. In the case of a sputtering target, if the density is lower than 5.0 g / cm ³ , DC sputtering becomes difficult and problems such as significant generation of nodules occur.
The target is based on a zinc oxide sintered body mainly composed of zinc oxide and mainly composed of a zinc oxide phase in which magnesium is dissolved, or gallium and / or aluminum mainly composed of zinc oxide. In addition, it is based on an oxide sintered body mainly composed of a zinc oxide phase in which magnesium is dissolved.

4). Production of Transparent Conductive Film The transparent conductive film of the present invention is formed on a substrate by a sputtering method or an ion plating method in a film forming apparatus using the target of the present invention. In particular, the direct current (DC) sputtering method is industrially advantageous and preferable because it has less thermal influence during film formation and enables high-speed film formation.

  That is, in the production of the transparent conductive film of the present invention, by using the target obtained from the oxide sintered body and adopting sputtering or ion plating conditions such as a specific substrate temperature, gas pressure, input power, etc. A method of forming a transparent conductive film made of zinc oxide containing magnesium or gallium and / or aluminum and zinc oxide containing magnesium on a substrate is used.

In order to form a transparent conductive film according to the present invention, it is preferable to use an inert gas such as argon as the sputtering gas and to use direct current sputtering. Further, the inside of the sputtering apparatus can be sputtered at a pressure of 0.1 to 1 Pa, particularly 0.2 to 0.8 Pa.
In the present invention, for example, after evacuating to 5 × 10 ⁻⁵ Pa or less, pure Ar gas is introduced, the gas pressure is set to 0.2 to 0.5 Pa, DC power 100 to 300 W is applied, and DC plasma is generated. And pre-sputtering can be performed. After performing this pre-sputtering for 5 to 30 minutes, it is preferable to perform sputtering after correcting the substrate position if necessary.

In the present invention, a film can be formed without heating the substrate, but the substrate can also be heated to 50 to 300 ° C., particularly 80 to 200 ° C. When the substrate has a low melting point such as a resin plate or a resin film, it is desirable to form the film without heating.
If the sputtering target produced from the oxide sinter of the present invention is used, a transparent conductive film excellent in chemical resistance and conductivity can be produced on a substrate by a direct current sputtering method. Therefore, the manufacturing cost can be greatly reduced.
A similar transparent conductive film can also be formed when an ion plating target (also referred to as a tablet or a pellet) prepared from the oxide sintered body is used. In the ion plating method, when a target as an evaporation source is irradiated with heat from an electron beam or arc discharge, the irradiated portion becomes locally high in temperature, and evaporated particles are evaporated and deposited on the substrate. At this time, the evaporated particles are ionized by an electron beam or arc discharge. There are various ionization methods. The high-density plasma-assisted deposition method (HDPE method) using a plasma generator (plasma gun) is suitable for forming a high-quality transparent conductive film. In this method, arc discharge using a plasma gun is used. Arc discharge is maintained between the cathode built in the plasma gun and the crucible (anode) of the evaporation source. Electrons emitted from the cathode are introduced into the crucible by magnetic field deflection, and are concentrated and irradiated on the local part of the target charged in the crucible. By this electron beam, the evaporated particles are evaporated and deposited on the substrate from the portion where the temperature is locally high. Since vaporized evaporated particles and O ₂ gas introduced as a reaction gas are ionized and activated in the plasma, a high-quality transparent conductive film can be produced.

5. Transparent conductive film The transparent conductive film of the present invention is formed on a substrate by sputtering or ion plating using the above target.
That is, a transparent conductive film manufactured by a sputtering method or an ion plating method using a target processed from the oxide sintered body, (1) containing zinc oxide as a main component and further containing magnesium A transparent conductive film containing magnesium at a Mg / (Zn + Mg) atomic ratio of 0.02 to 0.30, or (2) containing zinc oxide as a main component, further containing magnesium, gallium and / Or a transparent conductive film containing aluminum, containing (Ga + Al) / (Zn + Ga + Al) atomic ratio in a ratio of more than 0 and 0.09 or less, and magnesium in an Mg / (Zn + Ga + Al + Mg) atomic ratio of 0.00. It contains in the ratio of 02-0.30.

  Conventional zinc oxide-based transparent conductive films dissolve easily in ordinary acids and alkalis, have poor resistance to acids and alkalis, and are difficult to control the etching rate. There is a problem that high-definition patterning processing is difficult. Since the present invention uses a sputtering target or an ion plating tablet which can be used for high-speed film formation by an industrially useful DC sputtering method or ion plating method and hardly generates arc discharge, the electrical and optical characteristics are used. A zinc oxide-based transparent conductive film having high chemical resistance to acids and alkalis can be obtained without impairing the properties. In particular, a zinc oxide-based transparent conductive film exhibiting high chemical resistance can be obtained by controlling the film composition and crystal phase.

  Since the transparent conductive film of the present invention is formed using the oxide sintered body as a raw material, the composition of the oxide sintered body is preferably reflected. That is, a transparent conductive film containing zinc oxide as a main component and further containing magnesium, and containing magnesium in a ratio of Mg / (Zn + Mg) atomic ratio of 0.02 to 0.30, or zinc oxide Is a transparent conductive film further containing magnesium and gallium and / or aluminum, and containing (Ga + Al) / (Zn + Ga + Al) atomic ratio in a ratio of more than 0 and 0.09 or less, and magnesium. The Mg / (Zn + Ga + Al + Mg) atomic ratio is preferably 0.02 to 0.30.

  This transparent conductive film has excellent chemical resistance by containing zinc oxide as a main component and containing magnesium in the above composition range. When the magnesium content is less than 0.02 in terms of the Mg / (Zn + Mg) atomic ratio, the transparent conductive film does not exhibit sufficient acid resistance and alkali resistance, and when it exceeds 0.30, the crystal of the film Therefore, sufficient acid resistance cannot be obtained. However, the alkali resistance is better as the magnesium content is increased, and is sufficiently good even when it exceeds 0.30. When the magnesium content exceeds 0.30 and the crystallinity of the film is lowered, the conductivity is also impaired.

The transparent conductive film can further exhibit higher conductivity by containing gallium and / or aluminum having the above composition range. When the content of gallium and / or aluminum exceeds 0.09 in terms of the (Ga + Al) / (Zn + Ga + Al) atomic ratio, the crystallinity of the film is lowered, so that sufficient acid resistance cannot be obtained.
Furthermore, in order for this transparent conductive film to exhibit excellent chemical resistance and low specific resistance, the total content of gallium and / or aluminum is 0.01 to 0 in terms of (Ga + Al) / (Zn + Ga + Al) atomic ratio. It is even more preferable that the magnesium content is 0.05 to 0.18 in terms of the Mg / (Zn + Ga + Al + Mg) atomic ratio.
Furthermore, in order to obtain even lower specific resistance, as well as excellent acid resistance and alkali resistance, the composition of the transparent conductive film can be obtained by changing the total content of gallium and / or aluminum to (Ga + Al) / (Zn + Ga + Al) atomic ratio. 0.035 to 0.08, and the magnesium content is more preferably in the range of 0.098 to 0.18 in terms of the Mg / (Zn + Ga + Al + Mg) atomic ratio. It is known that a zinc oxide-based transparent conductive film can be crystallized even at room temperature and is oriented on the c-plane (002). However, it is clear that the transparent conductive film having the above composition range exhibits extremely strong orientation. It became. Compared with a transparent conductive film formed using a zinc oxide sintered body containing gallium or aluminum as a target, which is generally used, the peak intensity due to c-plane (002) reflection is a remarkably high value of about 2.5 times at maximum. It was shown in the present invention that the specific resistance and excellent chemical resistance can be obtained by the effect. In order to obtain such a strong crystal orientation, it is not possible to obtain only the above composition range of magnesium. In addition, it is essential that the amount of gallium be within the above composition range.
In order to obtain the above strong crystal orientation, it is preferable that the oxygen content in the film is low. That is, it is effective to reduce the oxygen content in the oxide sintered body, that is, in the target using the HP method in the molding / sintering process, and to form a film in a reducing atmosphere as much as possible.

In Patent Document 3, an AZO film in which MgO chip is attached to a ZnO: Al ₂ O ₃ 2 wt% sintered body target by RF magnetron sputtering as a film forming method, and Mg is added by so-called on-chip sputtering. (Example 2) is shown. However, it is generally known that MgO is very stable. In this method, a ZnO: Al ₂ O ₃ 2 wt% sintered body target portion is preferentially sputtered. According to the experiments by the present inventors, in the ZnO: Al ₂ O ₃ 2 wt% sintered body target, even when the majority of the erosion region to be efficiently sputtered is covered with the MgO chip, almost no Mg is added. It is clear that the ratio of Zn to Zn is only about 0.5% atomic concentration. Without using Mg as MgO and without using the above-described target of the present invention in which Mg is dissolved in a ZnO lattice, it is extremely difficult to obtain an AZO film to which an amount of Mg exceeding 1% is added. .

The transparent conductive film of the present invention is composed mainly of a zinc oxide phase having a hexagonal wurtzite structure described in JCPDS card 36-1451. In order to obtain high conductivity and excellent acid resistance, as described above. The crystallinity of the film is important.
That is, it is important that the c-plane of the zinc oxide phase having a hexagonal wurtzite structure is oriented parallel to the substrate. In particular, the peak intensity ratio between the c-plane (002) and a-plane (100) of the zinc oxide phase having a hexagonal wurtzite structure obtained by X-ray diffraction measurement defined by the following formula (B) is 50 % Or more is preferable, 70% or more is more preferable, and 90% or more is more preferable.
I [ZnO (002)] / (I [ZnO (002)] + I [ZnO (100)]) × 100 (%) (B)

  Here, I [ZnO (002)] is the (002) peak intensity of the zinc oxide phase having a hexagonal wurtzite structure obtained by X-ray diffraction measurement, and I [ZnO (100)] is The (100) peak intensity of a zinc oxide phase having a hexagonal wurtzite structure obtained by X-ray diffraction measurement is shown. When the ratio of peak intensities is less than 50%, conductivity is impaired and sufficient acid resistance cannot be obtained.

Further, when magnesium is included in excess of 0.30 in terms of the Mg / (Zn + Ga + Al + Mg) atomic ratio, or the oxide sintered body as a raw material includes a magnesium oxide phase or a composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium. And a composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum, magnesium oxide having a cubic rock salt structure or a composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium, and magnesium and aluminum The contribution of the composite oxide MgAl ₂ O ₄ phase is increased, and a zinc oxide phase having a cubic rock salt structure is formed in the transparent conductive film. It is preferable that the zinc oxide phase having a cubic crystal structure is not contained in the film because it not only increases the specific resistance of the transparent conductive film but also decreases the acid resistance. Even if the X-ray diffraction intensity ratio of the formula (B) is 50% or more, sufficient acid resistance cannot be obtained when a zinc oxide phase having a cubic structure is included.

The transparent conductive film of the present invention is used as a wiring material for a liquid crystal display or the like. For that purpose, it is important that patterning can be performed by wet etching using a photoresist. That is, in order to enable patterning by wet etching, a moderate etching rate in the range of 30 to 100 nm / min with respect to a weak acid organic acid (ITO-06N manufactured by Kanto Chemical Co., Ltd.) and a weak alkali On the other hand, it must be not etched.
Moreover, when using as a functional transparent conductive film, such as an antistatic use, minimum weather resistance is important. That is, it is necessary for a weak acid to have the same degree as described above and to exhibit an etching rate of 20 nm / min or less with respect to a weak alkali (5% KOH).
As described above, the transparent conductive film of the present invention uses a target obtained by processing an oxide sintered body in which magnesium is added to zinc oxide or gallium and / or aluminum is added in an appropriate composition range. Since it is produced by appropriately controlling the structure and crystallinity, it has excellent acid resistance and alkali resistance. Therefore, it is possible to sufficiently satisfy the above etching characteristics.

In this invention, since the film thickness of a transparent conductive film changes with uses, it cannot specify in particular, However, It is 20-500 nm, Preferably it is 100-300 nm. If the thickness is less than 20 nm, a sufficient specific resistance cannot be ensured. On the other hand, if it exceeds 500 nm, a problem of coloring of the film occurs, which is not preferable.
Moreover, the average transmittance | permeability in the visible region (400-800 nm) of a transparent conductive film is 80% or more, Preferably it is 85% or more, More preferably, it is 90% or more. When the average transmittance is less than 80%, application to an organic EL device or the like becomes difficult.

6). Transparent conductive substrate In the present invention, the above-mentioned transparent conductive thin film is usually formed on a substrate (substrate) selected from a glass plate, a quartz plate, a resin plate or a resin film, and has a transparent conductive property. It becomes a base material.

This transparent conductive substrate allows the transparent conductive film to function as an anode and / or a cathode of a display panel such as an LCD, PDP, or EL element. Since the substrate also serves as a light-transmitting support, it needs to have a certain strength and transparency.
Examples of the material constituting the resin plate or resin film include polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate (PAR), polycarbonate (PC), etc., and these surfaces are coated with acrylic resin. It may be a resin plate or a resin film having a structured structure.
The thickness of the substrate is not particularly limited, but is 0.5 to 10 mm, preferably 1 to 5 mm for a glass plate or a quartz plate, and is 0. 5 mm for a resin plate or a resin film. 1 to 5 mm, preferably 1 to 3 mm. If it is thinner than this range, the strength is weak and handling is difficult. On the other hand, if it is thicker than this range, not only the transparency is poor, but also the weight is unfavorable.

  Any of an insulating layer, a semiconductor layer, a gas barrier layer, or a protective layer composed of a single layer or multiple layers can be formed on the substrate. The insulating layer includes a silicon oxide (Si—O) film or a silicon nitride oxide (Si—O—N) film, and the semiconductor layer includes a thin film transistor (TFT), which is mainly formed on a glass substrate. The gas barrier layer is a water vapor barrier film such as a silicon oxide (Si—O) film, a silicon nitride oxide (Si—O—N) film, a magnesium aluminum oxide (Al—Mg—O) film, or a tin oxide-based (for example, (Sn—Si—O) film or the like is formed on the resin plate or resin film. The protective layer is for protecting the surface of the substrate from scratches and impacts, and various coatings such as Si-based, Ti-based, and acrylic resin-based are used. Note that the layer that can be formed over the substrate is not limited thereto, and a thin metal film having conductivity can be applied.

  The transparent conductive substrate obtained by the present invention has a transparent conductive film having excellent properties such as specific resistance, light transmittance, and surface flatness, so that it can be used as a component of various display panels. Very useful. Moreover, as an electronic circuit mounting component provided with the said transparent conductive base material, a laser component etc. other than an organic EL element can be mentioned.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

(Evaluation of sintered oxide)
The specific resistance of the obtained oxide sintered body was measured on the polished surface by a four-probe method. Moreover, the end material of the obtained oxide sintered body was pulverized, powder X-ray diffraction measurement was performed, and the generated phase was identified.

(Basic characteristic evaluation of transparent conductive film)
The film thickness of the obtained transparent conductive film was measured with a surface roughness meter (manufactured by Tencor). The specific resistance of the film was calculated from the product of the surface resistance and the film thickness measured by the four probe method. The optical properties of the film were measured with a spectrophotometer (manufactured by Hitachi, Ltd.). The formation phase of the film was identified by X-ray diffraction measurement (manufactured by PANalytical). In addition, the production | generation of the zinc oxide phase which takes a cubic rock salt structure was determined by the reciprocal lattice space mapping measurement using X-ray diffraction.

(Evaluation of chemical resistance of transparent conductive film)
A transparent conductive film having a thickness of about 200 nm was formed, and the chemical resistance was examined by the following procedure. About acid resistance, it immersed in the organic acid etching liquid ITO-06N (product made from Kanto Chemical) for ITO set to 30 degreeC for 20 second, and determined by the etching rate per minute calculated | required from the film thickness difference before and behind immersion. Similarly, the alkali resistance was determined by immersing in a 5% KOH aqueous solution for 1 minute and determining the etching rate per minute.

(Example 1)
An oxide sintered body containing zinc oxide as a main component and containing magnesium was produced as follows. A zinc oxide powder having an average particle diameter of 3 μm or less and a magnesium oxide powder having an average particle diameter of 1 μm or less are used as starting materials, respectively, and the magnesium oxide content is 0.10 in terms of Mg / (Zn + Mg) atomic ratio. It mix | blended so that. The raw material powder was put into a resin pot together with water and mixed by a wet ball mill. At this time, hard ZrO ₂ balls were used, and the mixing time was set to 36 hours. After mixing, the slurry was taken out, filtered, dried and granulated. The granulated product was molded by applying a pressure of 3 ton / cm ² with a cold isostatic press.
Next, the compact was sintered as follows. The temperature in the sintering furnace was raised to 1000 ° C. at a rate of temperature rise of 0.5 ° C./min with the atmosphere as air. After reaching 1000 ° C., oxygen was introduced into the atmosphere in the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of} the furnace volume, and kept at 1000 ° C. for 3 hours. Subsequently, the temperature was raised again to a sintering temperature of 1400 ° C. at a temperature rising rate of 0.5 ° C./min. When cooling after sintering, the introduction of oxygen was stopped, and the temperature was lowered to 1000 ° C. at 0.5 ° C./min to produce an oxide sintered body made of zinc oxide and magnesium. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 50 kΩcm or less. The density was 5.5 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a diffraction peak due to a magnesium oxide phase having a cubic rock salt structure was confirmed. There wasn't. Since the oxide sintered body does not contain gallium and aluminum, the diffraction peaks of the composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium and the composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum are No longer exists. That is, the peak intensity ratio defined by the formula (A) was 0%.
Such an oxide sintered body was bonded to a backing plate made of oxygen-free copper using metallic indium to obtain a sputtering target. The diameter was 152 mm and the thickness was 5 mm, and the sputtering surface was polished with a cup grindstone so that the maximum height Rz was 3.0 μm or less.
Using this as a sputtering target, film formation by direct current sputtering was performed. A sputtering target was attached to a cathode for a non-magnetic material target of a DC magnetron sputtering apparatus (manufactured by Anelva) equipped with a DC power supply having no arcing suppression function. As the substrate, an alkali-free glass substrate (Corning # 7059) was used, and the target-substrate distance was fixed at 46 mm. After evacuating to 7 × 10 ⁻⁵ Pa or less, pure Ar gas was introduced, the gas pressure was set to 0.2 Pa, DC power 300 W was applied to generate DC plasma, and pre-sputtering was performed. After sufficient pre-sputtering, a transparent conductive film was formed by placing a substrate directly above the sputtering target, that is, at a stationary facing position, and performing sputtering without heating.
Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. The diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure is only observed due to c-plane (002) reflection, and is defined by the formula (B). The a-plane (100) of the zinc oxide phase The c-plane (002) peak intensity ratio with respect to was 100%. When the specific resistance of the film was measured, it was 2.7 × 10 ⁻³ Ωcm.
Next, when the etching rate at the time of immersing the obtained transparent conductive film in ITO-06N was measured, it was 70 nm / min and showed the etching rate with respect to a moderate acid. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Comparative Example 1)
A conventional zinc oxide oxide sintered body doped with gallium was prepared. Zinc oxide powder and gallium oxide powder were used as starting materials, and were mixed so that the content as gallium was 0.05 in terms of Ga / (Zn + Ga) atomic ratio.
When the specific resistance value of the obtained oxide sintered body was measured, it was confirmed that it was 1 kΩcm or less. The density was 5.7 g / cm ³ . When the phase of the oxide sintered body was identified by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed.
The oxide sintered body was bonded to form a sputtering target, and film formation was performed by direct current sputtering. Arc discharge did not occur and stable film formation was possible.
The result of having identified the production | generation phase of the obtained transparent conductive film by X-ray diffraction measurement is shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only reflection by the c-plane (002) is observed, and the zinc oxide phase is defined by the formula (B) and is defined with respect to the a-plane (100). The peak intensity ratio of the c-plane (002) was 100%. Moreover, when the specific resistance of the film was measured, it was 8.3 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 560 nm / min. It was revealed that the etching rate was considerably higher than the appropriate etching rate, and the acid resistance was low. When immersed in 5% KOH, the etching rate was 180 nm / min, and it was revealed that the alkali resistance was low. The results are shown in Table 1.

(Example 2)
An oxide sintered body mainly composed of zinc oxide containing gallium and magnesium was produced. As starting materials, zinc oxide powder having an average particle diameter of 1 μm or less, gallium oxide powder having an average particle diameter of 1 μm or less, and magnesium oxide powder having an average particle diameter of 1 μm or less are used. Magnesium oxide was blended so that the content as magnesium was 0.02 in terms of Mg / (Zn + Ga + Mg) atomic ratio so that the / (Zn + Ga) atomic ratio was 0.005.
Sintering was carried out in the same manner as in Example 1, and the composition of the obtained oxide sintered body was analyzed. As a result, it was confirmed that it was almost the same as the blending composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.7 g / cm ³ . Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 2.0 × 10 ⁻³ Ωcm.
Next, when the etching rate at the time of immersing the obtained transparent conductive film in ITO-06N was measured, it was 90 nm / min and showed an etching rate with respect to an appropriate acid. When immersed in 5% KOH, it was 20 nm / min, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 3)
Except that the Ga / (Zn + Ga) atomic number ratio was changed to 0.08, the production method was the same as in Example 2, and the main component was zinc oxide containing gallium and magnesium, and Mg was Mg / (Zn + Ga + Mg) atomic ratio. As a result, an oxide sintered body containing 0.02 was prepared.
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.7 g / cm ³ . As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 1.9 × 10 ⁻³ Ωcm.
Next, when the etching rate at the time of immersing the obtained transparent conductive film in ITO-06N was measured, it was 90 nm / min and showed an etching rate with respect to an appropriate acid. When immersed in 5% KOH, it was 20 nm / min, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Comparative Example 2)
Except that the Ga / (Zn + Ga) atomic number ratio was changed to 0.10, the production method was the same as in Example 2, and the main component was zinc oxide containing gallium and magnesium, and Mg was Mg / (Zn + Ga + Mg) atomic ratio. As a result, an oxide sintered body containing 0.02 was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed to be 5 kΩcm or less. The density was 5.6 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target.
When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. Although the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure was only observed due to c-plane (002) reflection, the peak intensity of the zinc oxide phase was lower than that of Example 2. It was suggested that the crystallinity was reduced due to gallium excess. Nevertheless, the peak intensity ratio of the c-plane (002) to the a-plane (100) of the zinc oxide phase defined by the above-mentioned formula (B) was 100%. When the specific resistance of the film was measured, it was 6.1 × 10 ⁻³ Ωcm.
Next, the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured and found to be 420 nm / min. It was revealed that the etching rate was considerably higher than the appropriate etching rate, and the acid resistance was low. When immersed in 5% KOH, it was revealed that the etching rate was as high as 120 nm / min and the alkali resistance was not sufficient. It was speculated that the chemical resistance decreased due to the influence of the decrease in crystallinity of the zinc oxide phase having a hexagonal wurtzite structure due to the excessive content of gallium. The results are shown in Table 1.

(Comparative Example 3)
Zinc oxide containing gallium and magnesium was produced in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.08 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.01. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed to be 5 kΩcm or less. The density was 5.6 g / cm ³ .
As a result of phase identification of the oxide sintered body, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure or a composite oxide MgGa ₂ containing magnesium and gallium A diffraction peak due to the O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 1.6 × 10 ⁻³ Ωcm.
Next, when the obtained transparent conductive film was immersed in ITO-06N, the etching rate was measured and found to be 250 nm / min. It was revealed that the etching rate was higher than the appropriate etching rate, and the acid resistance was not sufficient. When immersed in 5% KOH, it was revealed that the etching rate was as high as 100 nm / min and the alkali resistance was not sufficient. It was speculated that sufficient chemical resistance could not be obtained due to insufficient magnesium content. The results are shown in Table 1.

(Example 4)
The main component is zinc oxide containing gallium and magnesium in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio is 0.05 and the Mg / (Zn + Ga + Mg) atomic ratio is 0.05. An oxide sintered body was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.6 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. The result of identifying the formation phase of the film by X-ray diffraction measurement is shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 1.5 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 9.7 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. As a result, the film was slightly etched, and the etching rate was 20 nm / min.

(Example 5)
Main component is zinc oxide containing gallium and magnesium in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio is 0.01 and the Mg / (Zn + Ga + Mg) atomic ratio is changed to 0.10. An oxide sintered body was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.5 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
The oxide sintered body was bonded to form a sputtering target, and film formation was performed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 9.8 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 6)
Zinc oxide containing gallium and magnesium was prepared in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.03 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.10. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.5 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 9.6 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 7)
Zinc oxide containing gallium and magnesium was prepared in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.05 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.10. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.5 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. The result of identifying the formation phase of the film by X-ray diffraction measurement is shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 2.0 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 9.8 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. Considering together with the results of Example 4, it is considered that the acid resistance and alkali resistance were further improved by the synergistic effect of having an appropriate composition of gallium and magnesium and having excellent crystallinity. .

(Example 8)
The main component is zinc oxide containing gallium and magnesium in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio is 0.05 and the Mg / (Zn + Ga + Mg) atomic ratio is 0.18. An oxide sintered body was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.4 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 2.2 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 1.0 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this way is considered to be due to the synergistic effect of having an appropriate composition of gallium and magnesium and having excellent crystallinity, as in Example 7. It is done.

Example 9
The main component is zinc oxide containing gallium and magnesium in the same manner as in Example 2, except that the Ga / (Zn + Ga) atomic ratio is 0.005 and the Mg / (Zn + Ga + Mg) atomic ratio is 0.30. An oxide sintered body was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.1 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As a diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, not only the c-plane (002) but also the a-plane (100) peak was observed. However, the peak intensity was low, and the ratio of c-plane (002) to a-plane (100) was 90%. Next, when the specific resistance of the film was measured, it was 2.3 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 80 nm / min and showed an appropriate etching rate. In the case of 5% KOH, it was 10 nm / min, and although it was slightly etched, sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 10)
Main component is zinc oxide containing gallium and magnesium in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio is 0.08 and the Mg / (Zn + Ga + Mg) atomic ratio is changed to 0.30. An oxide sintered body was prepared. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.1 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, not only the c-plane (002) but also the a-plane (100) peak is observed, and the ratio of the c-plane (002) to the a-plane (100) is 50%. When the specific resistance of the film was measured, it was 2.5 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 100 nm / min and showed an appropriate etching rate. When immersed in 5% KOH, the etching rate was 20 nm / min, and although it was slightly etched, sufficient alkali resistance was obtained. The results are shown in Table 1.

(Comparative Example 4)
The Ga / (Zn + Ga) atomic ratio is 0.08 and the Mg / (Zn + Ga + Mg) atomic ratio is 0.32 (0.27 is within the scope of claim 4 as in Comparative Example 5.) An oxide sintered body containing zinc oxide containing gallium and magnesium as a main component was produced by the same production method as in Example 2 except that the above was changed. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed to be 5 kΩcm or less. The density was 5.1 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, a diffraction peak due to a zinc oxide phase having a hexagonal wurtzite structure and a composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium was confirmed. It was. The ratio of the (311) peak intensity of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 25%. A diffraction peak due to a magnesium oxide phase having a cubic rock salt structure was not confirmed.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. In the initial stage of target use, arc discharge occurred somewhat, but relatively stable film formation was possible. However, as the use continued, the frequency of arc discharge increased and stable film formation became impossible. In the initial stage of using the target, it was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. In addition to X-ray diffraction measurement, the formation phase of the film was identified by reciprocal space mapping, and in addition to the zinc oxide phase having a hexagonal wurtzite structure, the presence of a zinc oxide phase having a cubic rock salt structure was found. confirmed. As for the diffraction peak of the zinc oxide phase having a hexagonal wurtzite structure, not only the c-plane (002) but also the a-plane (100) peak is observed, and the ratio of the c-plane (002) to the a-plane (100) is It was as low as 40%. When the specific resistance of the film was measured, it showed a high value of 6.7 × 10 ⁻³ Ωcm.
Next, the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured and found to be 310 nm / min. It was revealed that the etching rate was higher than the appropriate etching rate, and the acid resistance was not sufficient. Similarly, when immersed in 5% KOH, it was revealed that the etching rate was not so high as 20 nm / min and the alkali resistance was sufficient. Reduced acid resistance due to the formation of a zinc oxide phase with a cubic rock salt structure and a decrease in crystallinity of the zinc oxide phase with a hexagonal wurtzite structure due to excessive magnesium content I guess it was. The results are shown in Table 1.

(Example 11)
Except for shortening the mixing time by a wet ball mill to 24 hours, the production method was the same as in Example 2, and the main component was zinc oxide containing gallium and magnesium, and the respective contents were in a Ga / (Zn + Ga) atomic ratio. An oxide sintered body with 0.03 and Mg / (Zn + Ga + Mg) atomic ratio of 0.10 was produced.
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.0 g / cm ³ . Phase identification of the oxide sintered body by X-ray diffraction measurement revealed that, besides the zinc oxide phase having a hexagonal wurtzite structure, no magnesium oxide phase was confirmed, but it had a cubic rock salt structure. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase containing magnesium and gallium was confirmed. The (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 15%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Although arc discharge occurs very rarely, it does not cause a problem in use, and basically stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As a diffraction peak of the zinc oxide phase having a hexagonal wurtzite structure, not only the c-plane (002) but also a small a-plane (100) peak is observed, and the ratio of the c-plane (002) to the a-plane (100) Was 90%. When the specific resistance of the film was measured, it was 1.2 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 90 nm / min, which was an appropriate etching rate although faster than Example 6. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Comparative Example 5)
Magnesium oxide powder having an average particle size of about 5 μm is used as a raw material powder, the mixing time by a wet ball mill is shortened to 2 hours, the Ga / (Zn + Ga) atomic ratio is 0.08, and the Mg / (Zn + Ga + Mg) atomic ratio is An oxide sintered body containing zinc oxide containing gallium and magnesium as a main component was produced by the same production method as in Example 2 except that was changed to 0.32. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was 5 kΩcm or less. The density was 4.8 g / cm ³ .
Phase identification of sintered oxides by X-ray diffraction measurement revealed that in addition to a zinc oxide phase with a hexagonal wurtzite structure, a magnesium oxide phase with a cubic rock salt structure and a composite containing magnesium and gallium A diffraction peak due to the oxide MgGa ₂ O ₄ phase was confirmed. The ratio of the (311) peak intensity of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 45%.
The oxide sintered body was bonded to form a sputtering target, and direct current sputtering was performed. However, although the specific resistance of the oxide sintered body was low, arc discharge occurred frequently and stable film formation was not possible. The results are shown in Table 1.

Example 12
In order to add aluminum instead of gallium, except that gallium oxide powder was used instead of gallium oxide powder as a starting material, the production method was the same as that of Example 2, and the main component was zinc oxide containing aluminum and magnesium. An oxide sintered body was prepared in which Al is 0.005 as the Al / (Zn + Al) atomic ratio and Mg is 0.02 as the Mg / (Zn + Al + Mg) atomic ratio. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.6 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, including magnesium oxide phase with cubic rock salt structure or containing magnesium and aluminum A diffraction peak due to the composite oxide MgAl ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgAl ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 2.1 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 90 nm / min, which was an appropriate etching rate. Further, the etching rate when immersed in 5% KOH was 20 nm / min, and although it was slightly etched, sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 13)
In order to add aluminum instead of gallium, the Al / (Zn + Al) atomic ratio is 0.03 in the same production method as in Example 6 except that aluminum oxide powder is used instead of gallium oxide powder as a starting material. An oxide sintered body having a composition with an Mg / (Zn + Al + Mg) atomic ratio of 0.10 and mainly containing zinc oxide containing aluminum and magnesium was produced.
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.4 g / cm ³ . Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, including magnesium oxide phase with cubic rock salt structure or containing magnesium and aluminum A diffraction peak due to the composite oxide MgAl ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgAl ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 9.9 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 14)
In order to add aluminum in place of gallium, Al is mainly composed of zinc oxide containing aluminum and magnesium by the same production method as in Example 8 except that aluminum oxide powder is used instead of gallium oxide powder as a starting material. An oxide sintered body having a composition having a / (Zn + Al) atomic ratio of 0.05 and an Mg / (Zn + Al + Mg) atomic ratio of 0.18 was produced.
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.3 g / cm ³ . Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, including magnesium oxide phase with cubic rock salt structure or containing magnesium and aluminum A diffraction peak due to the composite oxide MgAl ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgAl ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 2.1 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 1.0 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. Considering together with the result of Example 4, it is considered that the acid resistance and the alkali resistance are further improved by the synergistic effect by having an appropriate amount of aluminum and magnesium and having excellent crystallinity. .

(Example 15)
Except for replacing part of the gallium added in Example 6 with aluminum and setting the Ga / (Zn + Ga) atomic ratio to 0.025 and Al / (Zn + Al) atomic ratio to 0.005, An oxide sintered body mainly composed of zinc oxide containing gallium, aluminum, and magnesium was manufactured by the same manufacturing method.
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.4 g / cm ³ . As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were added. Diffraction peaks due to the composite oxide MgGa ₂ O ₄ phase containing and the composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum were not confirmed. That is, the (311) peak intensity of the composite oxide MgGa ₂ O ₄ phase and the (311) peak intensity of the MgAl ₂ O ₄ phase with respect to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) The sum ratio was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. When the specific resistance of the film was measured, it was 1.1 × 10 ⁻³ Ωcm, which was slightly higher than Example 6.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 16)
The film forming method was changed to the ion plating method, and the same composition as in Example 6, that is, an oxide having a Ga / (Zn + Ga) atomic ratio of 0.03 and an Mg / (Zn + Ga + Mg) atomic ratio of 0.10 Film formation was performed using a tablet made of a sintered body. The method of manufacturing the oxide sintered body is substantially the same as that of Example 1, but as described above, when used as a tablet for ion plating, it is necessary to reduce the density. The sintering temperature was 1100 ° C. The tablet was molded in advance so that the dimensions after sintering were 30 mm in diameter and 40 mm in height. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 3.9 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, containing magnesium oxide phase with cubic rock salt structure or containing magnesium and gallium A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Using such an oxide sintered body as a tablet, a film was formed by an ion plating method. For the film formation, a reactive plasma vapor deposition apparatus capable of high density plasma assisted vapor deposition (HDPE method) was used. The film forming conditions were such that the distance between the evaporation source and the substrate was 0.6 m, the discharge current of the plasma gun was 100 A, the Ar flow rate was 30 sccm, and the O ₂ flow rate was 10 sccm.
When the oxide sintered body of the present invention was used as a tablet, stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the tablet. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The specific resistance of the film was measured and found to be 7.2 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 60 nm / min, which was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1.

(Example 17)
Zinc oxide containing gallium and magnesium was produced in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.065 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.115. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.4 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. The result of identifying the formation phase of the film by X-ray diffraction measurement is shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to the c-plane (002) reflection is one level higher than that of Example 4 similarly shown in FIG. 1, and is about 2.4 times higher than that of Comparative Example 1 in which magnesium is not added. It was. When the specific resistance of this film was measured, it was 8.8 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it showed much better acid resistance and was an appropriate etching rate of 40 nm / min. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this way was that the acid and alkali resistance were further improved by the synergistic effect due to the appropriate composition of gallium and magnesium and the excellent crystallinity. It is considered a thing.

(Example 18)
Zinc oxide containing gallium and magnesium was produced in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.06 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.098. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.5 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. The results are shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection is one step higher than that of Example 4 similarly shown in FIG. 1 and about 2.1 times higher than that of Comparative Example 1 in which magnesium is not added. It was. When the specific resistance of the film was measured, it was 8.9 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 50 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this way was that the acid and alkali resistance were further improved by the synergistic effect due to the appropriate composition of gallium and magnesium and the excellent crystallinity. It is considered a thing.

Example 19
Zinc oxide containing gallium and magnesium was produced in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.035 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.15. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.3 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to the c-plane (002) reflection is one level higher than that of Example 4 similarly shown in FIG. 1, and is about 1.9 times higher than that of Comparative Example 1 in which magnesium is not added. It was. When the specific resistance of the film was measured, it was 9.7 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 60 nm / min, which was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this way was that the acid and alkali resistance were further improved by the synergistic effect due to the appropriate composition of gallium and magnesium and the excellent crystallinity. It is considered a thing.

(Example 20)
Zinc oxide containing gallium and magnesium was produced in the same manner as in Example 2 except that the Ga / (Zn + Ga) atomic ratio was changed to 0.08 and the Mg / (Zn + Ga + Mg) atomic ratio was changed to 0.18. An oxide sintered body having a main component was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.3 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection is one step higher than that of Example 4 similarly shown in FIG. 1 and about 2.1 times higher than that of Comparative Example 1 in which magnesium is not added. It was. When the specific resistance of the film was measured, it was 9.8 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this way was that the acid and alkali resistance were further improved by the synergistic effect due to the appropriate composition of gallium and magnesium and the excellent crystallinity. It is considered a thing.

(Example 21)
Except for changing the Ga / (Zn + Ga) atomic ratio to 0.09, changing the Mg / (Zn + Ga + Mg) atomic ratio to 0.18, and further adding 0.2 wt% of titanium oxide as a sintering aid. An oxide sintered body mainly composed of zinc oxide containing gallium and magnesium was produced by the same production method as in No. 2. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.2 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 1.4 times that of Comparative Example 1 in which no magnesium was added. When the specific resistance of the film was measured, it was 1.2 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 70 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. As a result, etching began slightly, and the etching rate was 20 nm / min.
In addition, the influence of the sintering aid on the various characteristics of the film was not recognized.

(Example 22)
In order to add aluminum instead of gallium, except that gallium oxide powder was used instead of gallium oxide powder as a starting material, the production method was the same as that of Example 2, and the main component was zinc oxide containing aluminum and magnesium. An oxide sintered body in which Mg is 0.05 as the Al / (Zn + Al) atomic ratio and Mg is 0.098 as the Mg / (Zn + Al + Mg) atomic ratio was produced. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 5 kΩcm or less. The density was 5.4 g / cm ³ .
Phase identification of oxide sinter by X-ray diffraction measurement confirmed only zinc oxide phase with hexagonal wurtzite structure, including magnesium oxide phase with cubic rock salt structure or containing magnesium and aluminum A diffraction peak due to the composite oxide MgAl ₂ O ₄ phase was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgAl ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 2.2 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 2.1 × 10 ⁻³ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 50 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent properties were obtained in this way was that the acid resistance and alkali resistance were further improved due to the synergistic effect of having an appropriate amount of aluminum and magnesium and having excellent crystallinity. It is considered a thing.

(Example 23)
An oxide sintered body mainly composed of zinc oxide containing gallium, aluminum, and magnesium was produced by the same production method as in Example 15 except that the Al / (Zn + Al) atomic ratio was set to 0.025. .
When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.3 g / cm ³ . As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were added. Diffraction peaks due to the composite oxide MgGa ₂ O ₄ phase containing and the composite oxide MgAl ₂ O ₄ phase containing magnesium and aluminum were not confirmed. That is, the (311) peak intensity of the composite oxide MgGa ₂ O ₄ phase and the (311) peak intensity of the MgAl ₂ O ₄ phase with respect to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) The sum ratio was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. In addition, the input DC power was increased to 500 W and the number of abnormal discharges per 10 minutes was measured, but it did not occur at all. After the measurement, the state of generation of particles on the non-erosion part of the target surface was examined, but it was not generated at all.
It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. When the formation phase of the film was identified by X-ray diffraction measurement, it was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection was about 2.0 times as high as that of Comparative Example 1 in which magnesium was not added. When the specific resistance of the film was measured, it was 9.1 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it was 50 nm / min and was an appropriate etching rate. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. The reason why much more excellent characteristics were obtained in this manner is that, as in the case of gallium addition in Example 7, the gallium amount, the aluminum amount, and the magnesium amount have an appropriate composition and excellent crystallinity. This is probably due to a synergistic effect.

(Example 24)
Except that the production method was changed from the normal pressure firing method to the hot press method, the production method was the same as in Example 17, except that gallium was Ga / (Zn + Ga) atomic ratio of 0.065, and magnesium was Mg / (Zn + Ga + Mg). An oxide sintered body mainly composed of zinc oxide containing 0.115 in atomic ratio was prepared. The conditions of the hot pressing method were an argon atmosphere, a temperature of 1100 ° C., a pressure of 19.60 MPa (200 kgf / cm 2), and a pressing time of 1 hour. When the composition of the obtained oxide sintered body was analyzed, it was confirmed that it was almost the same as the blend composition. When the specific resistance value of the oxide sintered body was measured, it was confirmed that the specific resistance was 1 kΩcm or less. The density was 5.6 g / cm ³ .
As a result of phase identification of the oxide sintered body by X-ray diffraction measurement, only a zinc oxide phase having a hexagonal wurtzite structure was confirmed, and a magnesium oxide phase having a cubic rock salt structure, or magnesium and gallium were observed. A diffraction peak due to the composite oxide MgGa ₂ O ₄ phase contained was not confirmed. That is, the (311) peak intensity ratio of the composite oxide MgGa ₂ O ₄ phase to the peak intensity of the zinc oxide phase (101) defined by the above formula (A) was 0%.
Such oxide sintered bodies were bonded to form a sputtering target, and a film was formed by direct current sputtering. Arc discharge did not occur and stable film formation was possible. It was confirmed that the composition of the obtained transparent conductive film was almost the same as that of the target. The result of identifying the formation phase of the film by X-ray diffraction measurement is shown in FIG. It was composed only of a zinc oxide phase having a hexagonal wurtzite structure, and the presence of a zinc oxide phase having a cubic rock salt structure was not confirmed. As for the diffraction peak of the zinc oxide phase having the hexagonal wurtzite structure, only the c-plane (002) reflection is observed, and the a-plane of the zinc oxide phase defined by the above formula (B) ( The peak intensity ratio of c-plane (002) to 100) was 100%. The peak intensity due to c-plane (002) reflection is one level higher than that of Example 4 similarly shown in FIG. 1, and is about 2.7 times higher than that of Comparative Example 1 in which magnesium is not added. It was. When the specific resistance of this film was measured, it was 7.8 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive film was immersed in ITO-06N was measured, it showed much better acid resistance and was an appropriate etching rate of 30 nm / min. Etching was not performed at all with respect to 5% KOH, and sufficient alkali resistance was obtained. The results are shown in Table 1. In addition, about the alkali resistance by 5% KOH, the test on the severer conditions at the liquid temperature of 50 degreeC was also implemented. Even in the result, it was not etched at all and showed excellent alkali resistance. Thus, the reason why various characteristics more excellent than those of Example 17 were obtained is that, in addition to the synergistic effect due to the appropriate composition of gallium and magnesium, and the excellent crystallinity, the oxide It is considered that the oxygen content of the sintered body and the obtained film was reduced.

(Example 25)
A silicon oxynitride film having a thickness of 100 nm is formed in advance as a gas barrier film on a PES film substrate having a thickness of 100 μm, and a transparent conductive film having a film thickness of 200 nm is formed on the gas barrier film in the same manner as in Example 17. A conductive substrate was prepared.
The obtained transparent conductive substrate had crystallinity equivalent to that of Example 17, and the specific resistance was 8.5 × 10 ⁻⁴ Ωcm.
Next, when the etching rate when the obtained transparent conductive base material was immersed in ITO-06N was measured, it was an appropriate etching rate of 40 nm / min. It was confirmed that the film was not etched at all with respect to 5% KOH, and was not etched even under more severe conditions at a liquid temperature of 50 ° C., and had sufficient alkali resistance as in Example 17.

In Example 1, since the oxide sintered body contains zinc oxide as a main component and further contains a specific amount of magnesium, when this is used as a sputtering target, arc discharge is generated even in direct current sputtering. The transparent conductive film excellent in chemical resistance could be formed. Moreover, in Examples 2-10, Examples 12-15, and Examples 17-24, since it was set as the oxide sintered compact which contains a specific amount of gallium and / or aluminum, the electroconductivity of the obtained transparent conductive film is set. It turns out that it can improve further. In particular, in Examples 7 to 8, Example 14, Examples 17 to 19, 22 to 23, by making gallium and / or aluminum and magnesium into a specific composition range, and in Example 24, a sintering method is used. By adopting a hot press, the crystallinity of the film can be remarkably improved. As a result, not only the conductivity but also the chemical resistance can be further improved.
In Example 11, the density of the oxide sintered body obtained by changing the mixing time of the raw material powder was slightly reduced, but the chemical resistance and conductivity of the obtained transparent conductive film were not significantly affected. I understand that.
Furthermore, in Example 16, an oxide sintered body containing zinc oxide as a main component and containing specific amounts of magnesium and gallium was used as an ion plating target, but it was excellent in chemical resistance like sputtering. A transparent conductive film could be formed.
Moreover, in Example 25, the transparent conductive base material using the transparent conductive film excellent in chemical resistance was able to be obtained.

  On the other hand, Comparative Example 1 is a conventional gallium-doped zinc oxide sintered body to which magnesium is not added, and Comparative Examples 2 to 5 have magnesium and gallium added. Since it deviates from the scope of the invention, the chemical resistance and conductivity of the transparent conductive film obtained using this were insufficient. In Comparative Example 5, since the raw material powder having a large average particle diameter was used and the mixing time was extremely short, a magnesium oxide phase was generated in the oxide sintered body, and arc discharge was generated by sputtering, so that a transparent conductive film could be formed. There wasn't.

The oxide sintered body of the present invention is used as a sputtering target, and does not generate arc discharge even by direct current sputtering, and can form a transparent conductive film excellent in chemical resistance. Furthermore, the oxide sintered body containing a specific amount of gallium and / or aluminum can further improve the conductivity of the transparent conductive film obtained.
Further, the oxide sintered body of the present invention can be similarly used as a tablet for ion plating, and high-speed film formation is possible. The zinc oxide-based transparent conductive film of the present invention thus obtained is controlled to an optimal composition and crystal phase, and thus exhibits excellent chemical resistance without greatly impairing visible light transmittance and electrical resistivity. It is industrially extremely useful as a transparent conductive film that does not use relatively expensive indium and a transparent conductive substrate having the transparent conductive film.

Claims (25)

  An oxide sintered body containing zinc oxide and magnesium, wherein the magnesium content is 0.02 to 0.30 as the Mg / (Zn + Mg) atomic ratio.   2. The oxide sintered body according to claim 1, wherein the magnesium content is 0.05 to 0.18 as an Mg / (Zn + Mg) atomic ratio.   The specific resistance is 50 kΩcm or less, and the oxide sintered body according to claim 1 or 2.   Containing zinc oxide, magnesium, gallium and / or aluminum, and the content of gallium and / or aluminum is more than 0 and not more than 0.09 as (Ga + Al) / (Zn + Ga + Al) atomic ratio, An oxide sintered body characterized in that the magnesium content is 0.02 to 0.30 as the atomic ratio of Mg / (Zn + Ga + Al + Mg).   5. The oxide sintered body according to claim 4, wherein the magnesium content is 0.05 to 0.18 as an atomic ratio of Mg / (Zn + Ga + Al + Mg).   5. The oxide sintered body according to claim 4, wherein the content of gallium and / or aluminum is 0.01 to 0.08 in terms of (Ga + Al) / (Zn + Ga + Al) atomic number ratio.   The content of gallium and / or aluminum is 0.035 to 0.08 as the (Ga + Al) / (Zn + Ga + Al) atomic ratio, and the content of magnesium is 0.00 as the Mg / (Zn + Ga + Al + Mg) atomic ratio. It is 098-0.18, The oxide sintered compact of Claim 4 characterized by the above-mentioned. The oxide sintered body according to any one of claims 4 to 7, wherein a peak intensity ratio by X-ray diffraction measurement represented by the following formula (A) is 15% or less.
I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] / I [ZnO (101)] × 100 (%) (A)
(Where I [MgGa ₂ O ₄ (311) + MgAl ₂ O ₄ (311)] is the (311) peak intensity and MgAl ₂ O ₄ phase of the complex oxide MgGa ₂ O ₄ phase having a cubic rock salt structure (311) is the sum of peak intensities, and I [ZnO (101)] represents the (101) peak intensity of the zinc oxide phase having a hexagonal wurtzite structure)   The oxide sintered body according to claim 4, wherein the specific resistance is 5 kΩcm or less.   The oxide sintered body according to any one of claims 1 to 9, wherein a magnesium oxide phase is substantially not contained.   The oxide sintered body according to claim 1, wherein the oxide sintered body is obtained by molding and sintering by a hot press method.   A target obtained by processing the oxide sintered body according to claim 1. The target according to claim 12, wherein the density is 5.0 g / cm ³ or more, and the target is used in a sputtering method. The target according to claim 12, wherein the density is 3.5 to 4.5 g / cm ³ , and the target is used for an ion plating method.   A transparent conductive film formed on a substrate by sputtering or ion plating using the target according to claim 12.   16. The transparent conductive film according to claim 15, which contains zinc oxide and magnesium, and the magnesium content is 0.02 to 0.30 in terms of the Mg / (Zn + Mg) atomic ratio. .   It contains zinc oxide, magnesium, gallium and / or aluminum, and its content exceeds (Ga + Al) / (Zn + Ga + Al) atomic ratio of more than 0 and 0.09 or less, and the magnesium content is Mg / The transparent conductive film according to claim 15, wherein the atomic ratio of (Zn + Ga + Al + Mg) is 0.02 to 0.30.   The transparent conductive film according to claim 17, wherein the magnesium content is 0.05 to 0.18 as an atomic ratio of Mg / (Zn + Ga + Al + Mg).   19. The transparent conductive film according to claim 17, wherein the content of gallium and / or aluminum is 0.01 to 0.08 in terms of (Ga + Al) / (Zn + Ga + Al) atomic number ratio.   The content of gallium and / or aluminum is 0.035 to 0.08 in terms of (Ga + Al) / (Zn + Ga + Al) atomic ratio, and the content of magnesium is 0.00 in terms of Mg / (Zn + Ga + Al + Mg) atomic ratio. It is 098-0.18, The transparent conductive film of Claim 17 characterized by the above-mentioned. 21. The peak intensity ratio according to X-ray diffraction measurement represented by the following formula (B), which is mainly composed of a zinc oxide phase having a hexagonal wurtzite structure, is 50% or more. The transparent conductive film as described in 2.
I [ZnO (002)] / (I [ZnO (002)] + I [ZnO (100)]) × 100 (%) (B)
(Wherein I [ZnO (002)] is the (002) peak intensity of the zinc oxide phase having a hexagonal wurtzite structure, and I [ZnO (100)] has a hexagonal wurtzite structure. (Shows the (100) peak intensity of the zinc oxide phase.)   The transparent conductive film according to any one of claims 15 to 21, wherein a zinc oxide phase having a cubic rock salt structure is substantially not contained.   A transparent substrate and a transparent conductive film according to any one of claims 15 to 22 formed on one side or both sides of the transparent substrate, wherein the transparent substrate is a glass plate, a quartz plate, one side or both sides are gas barriers. A transparent conductive substrate, which is either a resin plate or a resin film covered with a film, or a resin plate or a resin film in which a gas barrier film is inserted.   The transparent gas according to claim 23, wherein the gas barrier film is at least one selected from a silicon oxide film, a silicon oxynitride film, a magnesium aluminum oxide film, a tin oxide film, and a diamond-like carbon film. Conductive substrate. The transparent resin according to claim 23, wherein the resin plate or resin film is made of polyethylene terephthalate, polyethersulfone, polyarylate, polycarbonate, or a laminated structure in which the surface thereof is covered with an acrylic organic material. Conductive substrate.

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